Polymers with pendant fluoroalkylsulfide groups

Abstract

Polymers having pendant fluoroalkylsulfide side chains and processes for their preparation by nucleophilic displacement of halides in preformed polymers using fluoroalkylthiols are disclosed which provide oil and water repellency and antisoil properties to substrates.

What is claimed is: 
     
       1. A polymer having pendant fluoroalkylsulfide groups and pendant alkylsulfide groups comprising the reaction product of: a) a thiol of Formula I   R.sub.f --(A).sub.d --B--S--H                              I     wherein:     R f  is a fully fluorinated straight or branched aliphatic radical of about 3 to about 14 carbon atoms optionally interrupted by at least one ether oxygen atom;   A is a divalent radical selected from the group consisting of --SO 2  N(R)--, --CON(R)--, --S--, and --SO 2  -- wherein R is H or an alkyl radical of 1 to about 6 carbon atoms;   d is 0 or 1; and   B is a divalent linear hydrocarbon radical --C n  H 2n  -- wherein n is from about 2 to about 12,   b) a thiol of Formula II   X--R'--S--H                                                II     wherein:     X is H, OH, --COOM, or --SO 3  M;   M is H, Na, K, or NH 4  ;   R' is a difunctional alkyl group selected from the group consisting of --(CH 2 ) m  --, --CH(COOH)--, and --CH 2  --CH(COOH)--; a difunctional aromatic group --C 6  H 4  --; or a difunctional heterocyclic group --C 5  NH 3  --; and   m is 1 to 18; and   c) a polymer containing chlorine or bromine substituted on carbon, or a chlorinated or brominated paraffin of a maximum of 12 carbons and of a molecular weight of at least 250.   
     
     
       2. A polymer having pendant fluoroalkylsulfide groups comprising the reaction product of: a) a thiol of Formula I   R.sub.f --(A).sub.d --B--S--H                              I     wherein:     R f  is a fully fluorinated straight or branched aliphatic radical of about 3 to about 14 carbon atoms optionally interrupted by at least one ether oxygen atom;   A is a divalent radical selected from the group consisting of --SO 2  N(R)--, --CON(R)--, --S--, and --SO 2  -- wherein R is H or an alkyl radical of 1 to about 6 carbon atoms;   d is 0 or 1; and   B is a divalent linear hydrocarbon radical --C n  H 2n  -- wherein n is from about 2 to about 12, and   b) a polymer containing chlorine or bromine substituted on carbon, or a chlorinated or brominated paraffin of a maximum of 12 carbons and of a molecular weight of at least 250.   
     
     
       3. The polymer of claim 2 further reacted with a thiol of formula II   X--R'--S--H                                                II     wherein:   X is H, OH, --COOM, or --SO 3  M;   M is H, Na, K, or NH 4  ;   R' is a difunctional alkyl group selected from the group consisting of --(CH 2 ) m  --, --CH(COOH)--, and --CH 2  --CH(COOH)--; a difunctional aromatic group --C 6  H 4  --; or a difunctional heterocyclic group --C 5  NH 3  --; and   m is 1 to 18;   yielding a polymer having pendant fluoroalkylsulfide groups and pendant alkylsulfide groups.   
     
     
       4. The polymer of claim 1, 2 or 3 wherein the polymer having chlorine or bromine substituted on carbon is selected from the group consisting of a homopolymer or copolymer of chlorine or bromine containing alkylene or arylene monomers, epichlorohydrine, chlorinated or brominated alkyl epoxides, chlorinated or brominated alkyl oxetanes, chlorinated or brominated alkyl siloxanes, chlorinated or brominated polyesters, and chlorinated or brominated polyolefins. 
     
     
       5. The polymer of claim 4 wherein the polymer having chlorine substituted on carbon is polyvinylchloride or poly(epichlorohydrin). 
     
     
       6. The polymer of claim 1, 2 or 3 wherein the pendant fluoroalkylsulfide is of the fonnula F(CF 2 ) p  (CH 2 ) n  S-- wherein p is 3 to 18 and n is 2, or a mixture thereof. 
     
     
       7. The polymer of claim 1 or 3 wherein the pendant alkylsulfide is selected from the group consisting of octadecyl mercaptan, thiophenol, 2-mercapto pyridine, 2-mercaptoethanol, mercaptoacetic acid and mercaptosuccinic acid, or a mixture thereof. 
     
     
       8. A process for the preparation of a polymer having pendant fluoroalkylsulfide groups and pendant alkylsulfide groups comprising reacting a polymer having chlorine or bromine substituted on carbon, or a chlorinated or brominated paraffin of a maximum of 12 carbons and of a molecular weight of at least 250 with: a) a thiol of Formula I   R.sub.f --(A).sub.d --B--S--H                              I     wherein:     R f  is a fully fluorinated straight or branched aliphatic radical of about 3 to about 14 carbon atoms optionally interrupted by at least one ether oxygen atom;   A is a divalent radical selected from the group consisting of --SO 2  N(R)--, --CON(R)--, --S--, and --SO 2  -- wherein R is H or an alkyl radical of 1 to about 6 carbon atoms;   d is 0 or 1; and   B is a divalent linear hydrocarbon radical --C n  H 2n  -- wherein n is from about 2 to about 12, and   b) a thiol of Formula II   X--R'--S--H                                                II     wherein:     X is H, OH, --COOM, or --SO 3  M;   M is H, Na, K, or NH 4  ;   R' is a difunctional alkyl group selected from the group consisting of --(CH 2 ) m  --, --CH(COOH)--, and --CH 2  --CH(COOH)--; a difunctional aromatic group --C 6  H 4  --; or a difunctional heterocyclic group --C 5  NH 3  --; and   m is 1 to 18;   yielding a polymer having pendant fluoroalkylsulfide groups and pendant alkylthio groups.   
     
     
       9. A process for the preparation of a polymer having pendant fluoroalkylsulfide groups comprising reacting a polymer having chlorine or bromine substituted on carbon, or a chlorinated or brominated paraffin of a maximum of 12 carbons and of a molecular weight of at least 250 with a thiol of Formula I   R.sub.f --(A)d--B--S--H                                    I     R f  is a fully fluorinated straight or branched aliphatic radical of about 3 to about 14 carbon atoms optionally interrupted by at least one ether oxygen atom;   A is a divalent radical selected from the group consisting of --SO 2  N(R)--, --CON(R)--, --S--, and --SO 2  -- wherein R is H or an alkyl radical of 1 to about 6 carbon atoms;   d is 0 or 1; and   B is a divalent linear hydrocarbon radical --C n  H 2n  -- wherein n is from about 2 to about 12;   in the presence of a base to yield a polymer having pendant fluoroalkylsulfide groups.   
     
     
       10. The process of claim 8 or 9 conducted in the presence of a phase transfer catalyst. 
     
     
       11. The process of claim 10 wherein the catalyst is selected from the group consisting of benzyltriethylammonium salts and tetrabutylammonium salts. 
     
     
       12. A method of improving the oil and water repellency or antisoil property of a polymer having chlorine or bromine substituted on carbon, or of a chlorinated or brominated paraffin of a maximum of 12 carbons and of a molecular weight of at least 250 comprising replacing at least 5 mole percent of the chlorine or bromine with pendant fluoroalkylsulfide groups of formula:   R.sub.f --(A).sub.d --B--S--     wherein:   R f  is a fully fluorinated straight or branched aliphatic radical of about 3 to about 14 carbon atoms optionally interrupted by at least one ether oxygen atom;   A is a divalent radical selected from the group consisting of --SO 2  N(R)--, --CON(R)--, --S--, and --SO 2  -- wherein R is H or an alkyl radical of 1 to about 6 carbon atoms;   d is 0 or 1; and   B is a divalent linear hydrocarbon radical --C n  H 2n  -- wherein n is from about 2 to about 12.   
     
     
       13. A method of improving the oil and water repellency or antisoil property of a substrate comprising application to a surface of the substrate an effective amount of a solution or emulsion of the polymer of claim 1, 2 or 3 and drying the substrate. 
     
     
       14. A method of improving the oil and water repellency or antisoil property of a nonfluorinated polymer or paraffin by melt blending or powder blending said polymer or paraffin with a polymer having pendant fluoroalkylsulfide groups of claim 1, 2 or 3. 
     
     
       15. The polymer of claim 1 or 2 wherein A is selected from the group consisting of --SO 2  N(R)--, --S--, and --SO 2  --. 
     
     
       16. The polymer of claim 1 or 3 wherein X is OH, COOM, or SO 3  M.